Method for solubilizing at least partially insoluble and gelatinized oils



Patented Sept. 18, 1951 METHOD Eon soLUBILIzINoAr LEASTPARTIALLYJNSOLUBLE AND GELATI- NIZED oms Max Kronstein, New Yor N. Y. NoDrawing. Original application July 8, 1949,

Serial No. 103,753. Divided and this application February 9, 1951,Serial No. 215,198

12 Glaims- (01. 106244) This invention relates to the solubilizing ofinsoluble and gelatinized, or at least partially insoluble or partiallygelatinized, wax type esters as they are generally known in the art;that is, higher fatty acid esters of high atomic polyhydroxyl alcoholshaving less than three OH groups.

This application is a division of my copending a-pplcation S. N. 103,753filed July 8; 1949, for Method for Solubilizing at Least PartiallyInsoluble and Gelatinized Waxes.

This invention further relates to the solubilizing of at least partiallyinsoluble or at least partially gelatinized oil-type esters; that is,higher fatty acid esters of polyhydroxyl alcohols having more than twoOH groups.

The present application is a continuation-inpart of my United Statesapplication Serial No. 748,665, now Patent Number 2,476,879, issued July19, 1949, wherein I have disclosed and claimed a method of solubilizingan at least partially insoluble and at least partially gelled oilselected from the group consisting of fixed oils and syntheticallyproduced oil-like esters of a higher fatty acid which comprises meltingand compounding with said oil, a compound comprising a metal soap or acompound selected from the group consisting of higher fatty acids,high"- er fatty acid esters, petroleum acids and rosin acids, at amelting temperature below the decomposition temperature of the resultingcomposition and at such melting temperature that substantially theentire mass of the resulting composition is melted into the liquidstage, whereby to form a soluble fixed oil reaction product which iscapable of forming a stable solution. This application, Serial No.748,665 is in turn a continuation-in-part of my abandoned applicationSerial No. 496,262.

Reference is hereby made to my pending application Serial No. 33,676,wherein I have dis- 1 closedand claimed a method of insolubilizing andsolidifying fatty acid esters of alcohols which comprises treating saidesters with a potentially, free oxygen-yielding compound forming a metalsoap with said esters, at a temperature sufficiently elevated to elfectrelease of said free oxygen in said esters whereby to form a solidifiedcomposition which is insoluble in coal tar and petroleum solvents. Thusin the latter application, Serial No. 33,676, I have disclosed that theformation of an at least partially insoluble state is not limited to thepolyhydroxyl alcohol fatty acidesters (having-more than two OH groups).Of .the type disclosed incapable of 1 Serial No. 748,665, but I haveadditionally disclosed a process for at least partially solidifying suchproducts which are derived from alcohols having less than 3 hydroxylgroups.

Thus the present application presents a process for solubilizing andutilizing the esters of polyhydroxyl alcohols having less than threehydroxyl groups. More specifically, the present application is primarilyconcerned with the solubilization of a class of natural and syntheticsubstances known as waxes. It is dimcult to specifically define a waxbecause of the range of products to which the term is applied, althoughfor present purposes the waxes may be regarded as consisting chiefly ofhigher fatty acid esters of monoand dihydroxy high atomic alcohols,associated with one or more of the free fat and wax acids, freemonohydric alcohols and sterols, hydrocarbons, and lactones or othercondensation compounds. See The Chemistry and Technology of Waxes byWarth, 1947.

Thus, wax-forming esters such as cetyl palmitate are regarded as waxes.Waxes are generally referred to as being of insect, vegetable, animal,semi-mineral or mineral origin. The waxes of mineral origin are known asunsaponifiable waxes which consist largely of hydrocarbons; e. g.,ozokerite and ceres in. The mineral waxes and parafiin waxes consist ofa group of hydrocarbons related to methane and are therefore notproperly definable as waxes in that they do not consist primarily ofhigher fatty acid esters of monoor dihydric high atomic alcohols andhigher fatty acids.

In contrast to these unsaponifiable hydrocarbon mineral waxes, the waxesgenerally known assemi-mineral waxes comprise mostly esters of highmolecular weight alcohols and acids, plus free acids. Accordingly, thesemi-mineral waxes, such as montan wax, are properly classifiable asnatural vegetable type waxes such as carnauba or candelilla type waxeswhich are incompletely saponified with alkali (see page 6 of the bookletWaxes by American Cyanamid and Chemical Corp). Accordingly, semi-mineralwaxes of the montan type come within the purview of the presentinvention; whereas, mineral and paraffin waxes do not come within thepurview of the present invention.

It is known that the most desirable bases for use in preparing coatingcompositions are those which produce coating having a minimum degree ofswelling. The swelling capacity of a material is characterized by thefact that the swelling is connected with anincrease in volume condition.Thus gelatinized waxes have hereto-v fore been of little use in thecoating arts.

It has been observed that such materials which are used in a swollencondition, as for instance highly polymerized waxes, undergo shrinkingwhile drying and that during the drying or in the shrunken condition,such materials lose most of their ability to swell, probably by virtueof oxidation, polymerization or other chemical action. One possibleexplanation is that the components of such materials are apparentlyconnected to each other in a special manner and in a different mannerthan are the molecules of other materials which are readily solubleinthe usual thinners or varnish solvents.

An object of the present invention i to provide a process for treatingat least partially insoluble, gelatinous, swollen waxes so that they arecapable of being applied by coating or covering methods, as by brushing,spraying, dipping, or extruding, and can further be compounded withoutthe necessity of being returned to a nonswelling condition.

tially insoluble, gelatinous wax base composition.

Still another object of the invention is to provide a process formodifying the coating characteristics of waxes so as to bring them intoa swelling or swollen condition where they can be readily Worked up ordissolved into a liquid state,

and in which condition they can be stored indefinitely and then can beused directly and can be readily worked up or dissolved into a liquidstate, and in which condition they can be stored indefinitely and thencan be used directly and can be readily diluted for use as a coatingcomposition.

A still further object of the invention i to provide a wax base coatingcomposition which will have desirable coating or coveringcharacteristics, such as a high degree of elasticity, re-- sistance tohardening, aging, changes in temperature and changes in humidity, andwhich can be modified by compounding with resins, asphalts, phenolicresins, alkyd resins and other synthetic resinous materials, copal gums,natural or synthetic fixed oils of the type disclosed in my aforesaidapplication Serial No. 748,665, and the like.

Still another object of the. invention is to provide a process forsolubiliz-ing gelatini'zed wax compounds in the presence of naturalgums, resins, asphalts and. other natural materials thereby obtaininguseful compounds of solubilized gels with the natural material.

Still another object of the invention is to provide a process forsolubilizing those insoluble waxes which are incapable of formingcoherent film-like substances, so that they may be used subsequently asfilm-forming coatings.

Still another object is to provide a process'for 4 solubilizinggelatinized wax compounds in the presence of synthetic resinouscompounds such as phenolic resins or alkyd resin thereby obtaininguseful compounds of such solubilized gels with synthetic resinousmaterials.

Still another object is to providea process for solubilizing gelatinized.wax compounds in such manner that the products can be dissolved insolvents and plasticizers for use in lacquers, cellulose derivatives andvinyl compounds, and can be dissolved readily in polymerizable liquidsor solutions, such as styrene or the like to form stable solutions.

Another object of the invention is to provide a process for increasingthe swelling capacity of swollen or swelling waxes, to such an extentthat 7 they can be worked up in the usual thinners and varnish solvents.

These and other objects of the invention will be readily understood byreference to the following description:

products, preferably formed by reacting a wax,

fixed oil, fatty acid, a petroleum acid, a rosin acid, or mixturethereof with a compound of a metal-capable of reaction with such waxes,oils, fatty acids, rosin acids, naphthenic acids or other organiccompounds to form a corresponding wax soluble metal soap-like reactionproduct can be usedto solubilize and influence the degree of swelling ofwaxes which are at least partially insoluble and in a stage of swellingor are partially swollen, or which are completely swollen and 'in aninsoluble condition.

I have discovered further that gelatinized or at least partiallyinsoluble waxes can be solubilized by melting and compounding therewithcertain metallic soap-like reaction products by subjecting the mixtureto a melting temperature such that substantially the entire mass of theresulting composition is melted into the liquid stage thereby forming asoluble wax which is capable of forming a stable solution.

I have also discovered that the above-discovered process may bepracticed'with success by utilizing a metallic soap-like reactionproduct which is at least partially soluble and which is in a liquidstate at the melting'temperature of the above set forth process.

According to my invention, waxes, which are insoluble or at leastpartially insoluble, may be solubilized by melting and reactingtherewith,

-at"a temperature below the'decomposition temperature' of the resultingcompound, a metal soap-like reaction product.

By insoluble I mean to include the character: ization of any compoundwhich is incapable of dissolving in a liquid to form a stable. homoge.neous mixture.

a film.

By solubilizing I mean to include the treatment of any insoluble or atleast partially insoluble material to the extent that it will be capableof mixing with a liquid to form a' stable, homogeneous solution. V

By metal soap-like reaction product I mean to include any alkali,alkaline-earth, or heavy metalcompound of a complex organic acid or 5ester thereof, which is at least partially soluble in a waxor fixed oil.

By stable I mean to include any compound or solution which will remainin a balanced condition of miscibility which is not readily destroyed.

It is possible that the metal soap-like reaction products of the presentinvention may influence the degree of swelling without producing achemical reaction. In preparing a contact substance, that is, a metalsoap-like reaction product in accordance with the present invention,waxes, oils or their acids or mixtures of such materials are treated inthe presence of compounds such as metallic peroxides, acetates, oxides,hydroxides, carbonates, borates, or other inorganic or organic metalsalts, at a temperature which is sufficiently elevated to cause areaction to take place between the material and the metal compound so asto form the corresponding metal soap-like reaction product. Theresulting reaction product is clearly distinguished from other chemicalsubstances by its ability to raise the swelling capacity of insoluble,gelatinous swollen or swelling waxes, when compounded therewith, to suchan extent that the resulting composition can be worked up in the usualthinners or varnish solvents. It will be understood that the insoluble,gelatinous swollen or swelling waxes which are treated with the metalsoaplike contact substance in accordance with the present invention mayresult from heating, distillation, polymerization, oxidation,condensation such as the phthalic acid reaction, the action of sulphur,or of accelerators such as sulphur chlorides, boron fluorides, tintetrachlorides, or other chemical action, or from various combinationsof such reactions.

The exact nature of th compounding of the contact substance with theinsoluble, gelatinous swelling or swollen waxes is not clearlyunderstood. However, it is believed that the compounding results in theformation of a solution or in the formation of a condition of unlimitedswelling. It has been found that alkali, alkaliearth, and heavy metalsselected from each of the groups of the periodical system may beutilized to form metallic soap-like reaction products which may be usedsuccessfully as contact substances in practicing the present invention.

In the practice of the present process the relation between theinsoluble gelatinized, swellillg wax and the contact substance dependsin part upon the degree of swelling of the insoluble, gelatinized wax.If the gelatinized wax is in condition to be readily swelled, only aminimum amount of contact substance is required; whereas a greateramount is necessary if the gelatinized wax is in a condition which maynot be readily swelled. Thus, it has been found that fresh gelatinizedwaxes require a smaller portion of contact substance than is requiredfor gelatinized waxes which are in an aged condition. Likewise, certainwaxes, which have been highly gelatinized by continued heating,distillation or vacuum treatment, require an increased amount of contactsubstance. Waxes which have been altered or modified by the removal ofthe nongelatinized components also require an increased amount ofcontact substance.

While it has been found that an excess amount of contact substance maybe used for obtainin certain desired chaarcteristics, the proportionsset forth in the following examples are preferred. In a furtherembodiment of the invention, it has been found that the process ofliquefying the gelatinous compound with a metal soap-like reactionproduct may be promoted or accelerated by adding a non-gelatinous oil,wax or other material which is liquid at the temperature of the reactionand has the properties of acting as a solvent for the metal soap-likereaction product and as a sweller for the gelatinous compound.

In another embodiment of the invention, it has been found that freeacids contained in the soap-like reaction products may be removed orneutralized by heating them with borates, such as manganese or calciumborate and that such treatment does not interfere with the nature of theliquified gelatinous material.

It further has been found that sedimentations or impurities can beremoved by filtering, settling or centrifuging without thereby removingthe liquified gelatinous material from the compound.

It further has been found that the process of. compounding thegelatinous compounds with the metal'soap-like reaction'product may beaccom-- panied by a secondary process. Thus, in liquifying gelatinousproducts containing sulphur with metalsoap-like reaction products, theprocess of liquefying proceeds parallel with the forming of metalsulphides which can be removed subsequently from the liquefaction.

For purposes of clarity, the various natural and synthetic fatty acidesters of polyhydroxyl al-- cohols having three or more hydroxyl groupswill. be referred to as the oil-type esters, whereas thevarious naturaland synthetic fatty acid esters: of polyhydroxyl alcohols having lessthan three: hydroxyl groups will be referred to as the wax-- typeesters. i Thus, certain of the following examples relate to a preferredprocess for the preparation of a metallic soap-like contact substance bycom pounding natural or synthetic materials of the wax-type or naturalor synthetic materials of the oil type, or both, with metal soap-formingmetals, metal oxides, or metal salts, which resultant reaction productsare used as a contact substance for solubilizing an at least partiallyinsoluble gelatinized wax-type material. Additionally, the wax-typecontact substance may be used. for the solubilization of at leastpartially insoluble, gelatinized oil-type materials. Thus, the foregoingobjects should be understood to cover the solubilization of natural orsynthetic oils which are in an at least partially gelled and in at leastpartially insoluble state by heating and compounding therewith a metalsoap of a wax type substance.

Example 1 The following examples illustrate the use of materials of thewax-type for preparation of the metal soap-like contact substance forinsolubiliz ing and solubilizing purposes.

(a) 50 parts of carnauba wax, a natural plant wax, were heated with tenparts of chromium carbonate at about C. and above, the carbonic acid gasescaped under foaming. Heating was continued until the reaction sloweddown, which in this instance occurred at about 270 C. Upon cooling thereaction product appeared as a solid greenish substance. This contactsubstancewas subsequently used for solubilization as illustrated insubsequent examples.

(1)) 50 parts of shellac wax, a natural animal wax, were heated with tenparts red lead oxide. Heating was continued until reaction occurred atabout 100 C. Heating was then continued up to 250 C. and ametalsoap-like contact substance wasaiobtainedwhich upon cooling to room.temperature appeared as a dark'brownsolid material.-

(c) 50 parts of montan wax, a natural lignite wax, also referred to asa'semi-mineral wax, were heated with 12 parts zinc formate which wereadded to the wax melt at around 110 C. Foaming occurred up to about 160C., at which temperature the foaming subsided somewhat. Heating wascontinued with the occurrence of strong foam formation around 235 C.Heating was slowly continued up to about 275 C. Upon cooling to roomtemperature, a metal soap-like contact substance was obtained.

(d) In a modification of Example 1 above, 60 parts of montan wax wereheated in a similar manner with 20 parts lithium carbonate and heatingwas continued up to around 270 C., at which point the contact substancewas obtained.

(e) 31 parts of polyethylene glycol-di-triricinoleate, a syntheticwax-type substance. were heated with parts of cobalt acetate. Strongfoaming developed around 100 C. and at around 150 C., a bluish liquidstate was obtained and a slight waxlike form was observed in the areawhere the compound was in contact with the relatively cool air of theroom. Heating was continued at around 200 C., the film was no longerobserved and a uniform melt of brownish shade was obtained. Heating wascontinued somewhere slightly beyond 220 C. at which stage a semisolidcontact substance was obtained upon cool- (i) In a similar manner, 45parts candelilla wax were heated with 5 parts chromium carbonate.Foaming was most evident between 95 and 125 0., heating being continuedup to around 280 C. The reaction product had an appearance similar tothe product of Example ((1) and was used subsequently for liquefyingsolid waxes and oils.

(g) 42 parts ouricuri wax were heated with parts nickel sulphate and thereaction was car- ?ied up to about 280 C. A dark brown colored reactionproduct was obtained and used in a later example for the liquefyingprocess.

(It) 58 parts of Japan wax were heated with 5 parts lithium hydroxide.After a quickly beginning foam formation, the heating was carriedgradually up to around 275 C. Since some unreacted substance wasobserved, the melt was filtered through cheesecloth and a clear liquidwas obtained which later hardened in cooling.

The product was used as a contact substance in a later example forliquefying solid oil and wax.

(i) 39 parts of Japan wax were reacted in heating with 6 parts silvernitrate. The reaction occurred around 220 C. The product remainedcloudy, and Was used in later examples as a contact substance.

(7') 20 parts Japan wax were heated with 6 parts aluminum sulfate. Aliquid was formed initially and thereafter the natural wax portion ofthe compounded mixture combined with the aluminum salt to form a solidreaction product which remained solid up to 250 C. The remainder of thecompounded mixture formed a liquid metal salt product which was thenseparated from the solid matter by filtration. Upon cooling, the liquidportion became a soft wax-like material which was subsequently used as acontact substance in the succeeding examples disclosing actualliquefaction.

(k) 20 parts of Japan'wax were reacted under heating withdpartscupric-oxalate... Heat:

continued up to about 270 C. A medium ing was continued under occasionalstirring up to and above 245 C. A greenish cloudi product was obtainedwhich was used in a following example as a contact substance inliquefying at least partially insoluble substances.

(1) 27 parts of beeswax were reacted with 4.5 parts bismuth benzoate byheating and compoundingfor about 30 minutes up to around 250 C. Alightyellowish brown reaction "product was obtained.

(m) 25 partsbeeswax were heated and reacted with 5 parts manganeseoxalate, heating being brown reaction product was obtained.

(n) 20 parts ouricuri wax were heated and reacted with 6 parts zincbenzoate upon heatin up to around 255 C. a reddish dark brown productwas obtained.

(0) 18 parts carnauba wax were heated and compounded with 3 parts basicaluminum acetate up to about 280 C. A brownish wax-like product wasobtained.

(p) 30 parts polyethylene-glycol di-tri-ricinoleate, a syntheticwax-type composition were heated and reacted with 5 parts chromiumoxalate. A brownish compound was formed under foaming during the heatingwhich was continued up to around 275 C.

(q) 12 parts carnauba wax were heated and reacted with 2 parts magnesiumcarbonate and under foaming, a brownish compound was obtained. Theheating was continued up to around 255 C.

(r) 5 parts candelilla wax were mixed with 15 parts China-wood oil andthe mixture was. heated and reacted with 4 parts magnesium carbonate upto 255 C. The reddish brown product was subsequently used as a contactsubstance.

(s) 17 parts of beeswax were reacted with 3 parts antimony trioxideunder gradual heating and stirring up to about 270 C. A greyish browncontact substance was obtained. 7

(t) 42;parts liquid polyethylene glycol 400 ditriricinoleate were heatedand compounded with 7 parts zinc formiate. Heating was carried to about260 C.

(u) 15 parts ouricuri wax were heated and reacted with 3. parts aluminumborate. Very strong foaming was observed initially but the reactionsubsided and heating was discontinued around 270 C.

(v) 25 parts diethylene glycol monolaurate, a synthetic wax typecomposition, was heated with 5 parts cobalt acetate up to about 240 C.for about 15 minutes.

. Example 2 The following examples illustrate the utilization of thewax-type reaction products as formed by the methods set forth in thepreceding examples, either alone or in a mixture with minor amounts ofoil-type reaction products as disclosed in the aforementionedapplication S. N. 748,665, for the solubilization of at least partiallyinsoluble oil-type materials.

(a) This example discloses the solubilization of a natural oil gel witha contact substance derived from a natural wax made in accordance withthe preceding example: 7

20 parts of gelatinized linseed oil, which was at least partiallyinsoluble and incapable of forming a stable solution with solvents suchas petroleum naphtha or coal tar solvents, were heated with'ten parts ofthe carnauba wax-type contactasubstance.- set forth the. preceding.

Example 1 (a). Heating was continued to about 200 C. at which point aliquefied appearance was noticed. Heating was continued under stirringup to a temperature of 270 C. At this point, and the point of cooling,the resulting composition was capable of being completely dissolved inthe usual solvents. Thus, in this instance, 1 part of the resultingcomposition wassubstantially completely dissolved in 1.5 parts oftoluene. The dissolved solution was then filtered and stored. Followingseveral days storage, the solution was further diluted with 2 additionalparts toluene and subsequently with 2 parts VMP petroleum naphtha,thereby illustrating that other solvents can be used for the solution ofthe resulting composition. It is desired to point out that theaforementioned solvents are normally used for dissolving ungelatinizednatural oils.

(b) This example illustrates the liquefaction or solubilization of agclatinized natural oil by melting and compounding therewith a contactsubstance derived from a synthetic wax product.

40 parts of gelatinized soybean oil were heated with 20 parts ofpolyethylene glycol-di-tri-ricinoleate contact substance as formed inthe preceding Example l(c). The melting and compounding was carried outas in Example 2(a) above until liquefaction and solubilization wasobtained at around 215 C. and thereafter heating was continued to about270 C. After cooling, the resultant composition was dissolved in a ratioof one part to two parts of toluene and a stable liquefaction wasobtained in the form of a true solution.

This example illustrates the solubilization of a solid natural oil witha natural wax contact substance in the presence of a soluble oil.

Ten parts of solid linseed oil prepared (in accordance with the methoddescribed and claimed in my co-pending application Ser. No. 33,676) bytreatment with a potentially, free, oxygen-yielding compound incapableof forming a metal soap, at a temperature sufiiciently elevated toeffect the release of the free oxygen; in this instance benzoylperoxide. The resultant solidified linseed oil was insoluble in coal tarand petroleum solvents. The ten parts solid linseed oil were heated with5 parts of a shellac wax-type .contact substance prepared in accordancewith Example 1(b) above in the presence of parts of soluble bodiedlinseed oil known commercially as type Z-2. The soluble oil was added asa wetting agent in order to increase the effect of the contact substanceon the dry solid linseed oil. The mixture was compounded and heateduntil liquefaction occurred at around 250 to 265 C. The product was thenthinned in a one to one ratio with petroleum naphtha and was furtherdiluted by adding one part toluene to 5 parts of the naphtha solution. Astable soluble solution resulted. It will be apparent that theliquefaction may be accelerated by reducing the particle size of thesolid linseed oil, as by breaking up the initial solid material intosmall chunks and particles.

((1) This example illustrates the liquefaction of an at least partiallyinsoluble gel of a synthetic oil with a wax-type contact substance. 12parts gelled dehydrated caster oil, known commercially as Castung oil103, were heated and compounded with 5 parts of the contact substanceproduced in Example 1 (0) above from a synthetic wax. Liquefaction wasreached at about 240 C. and the compound was further heated to about 265C. and was thereafter dissolved in a one to one ratio with a xylenesolvent.

(e) A similar effect as in the preceding example was obtained fromgelled dehydrated castor oil by heating and compounding 10 parts of thisgel with two parts of a natural lignite wax-type contact substance asproduced in Example 1(a). Liquefaction was obtained at around 240 C. andheating was continued to about 270 C. The resulting composition wasdissolved in about 20 parts of a hydrated solvent known commercially asDekalin.

(f) This example illustrates the liquefaction of a solid modifiedpolyhydroxyl alcohol fatty acid and phthalic anhydride ester, which maybe identified as a solidified at least partially insoluble alkyd resin.20 parts of a solid alkyd resin prepared by solidifying a commercialnon-drying type oil-modified alkyd resin known commercially as Rezyl92-5 by a compounding heat treatment with benzoyl peroxide, were heatedwith 10 parts of montan wax type substance as prepared in Example 1(0)above. The compounding and heating was performed in the presence of 6parts soybean oil, liquefaction being obtained around 235 C., andheating continued up to around 280 C. The resulting composition wascompletely dissolved in equal parts toluene.

(g) This example illustrates the liquefaction of an at least partiallyinsoluble oil gel with a mixture of contact substances, one bein derivedfrom an oil and the other being derived from a wax.

50 parts gelatinized perilla oil were liquefied by heating andcompounding with a mixture of 5 parts contact substance obtained byreacting 93 parts linseed oil and 5 parts lead acetate together with 3parts of the wax-type contact substance of Example 1(a) above.Liquefaction was obtained at around 225 C. and heating was continued ataround 275 C. The product was substantially completely dissolved inabout 1 parts benzol.

(h) 12 parts heat-gelled linseed oil, which was partially insoluble andincapable of forming a stable solution with solvents, were resolubilizedby heating and compounding with 4 parts of the contact substanceobtained from Japan wax and aluminum sulfate as described in precedinExample 1(7') The liquefied substance obtained at around 270 C. was of arelatively light color. It was completely diluted with 20 parts toluene.An application on a steel panel produced a resistant and glossy coatingon baking at 105 C. for 45 minutes.

(2') 18 parts of a gelled dehydrated castor oil, which was partiallyinsoluble and incapable of forming a stable solution, were liquefied byheating and compounding with 10 parts of the metal soap-like reactionproduct produced in preceding Example from Japan wax and cupric oxalate.Liquefaction was obtained at around 260 C. and the product wascompletely thinned with 20 parts tetra-hydro-naphthalene (Tetralin).

(7) In a manner similar to Example c, 10 parts solid linseed oil asdescribed in Example 0 above, were liquefied by heating with 7 parts ofa contact substance comprising the reaction product as derived fromExample 1(h), by heating and compounding 58 parts of Japan wax as inExample 0 with 5 parts lithium hydroxide. Liquefaction was obtainedaround 280 C. and heating was continued up to 300 C. The product wascompletely thinned in 20 parts toluene.

(k) In a similar manner, 15 parts solid linseed oil were liquefied byheating and compounding 7 with 25 parts of the metal soap-like reactionproduct of Japan wax and silver nitrate described in Example 1(2').Liquefaction was obtained at around 260 C. and heating was continued upto 300 C. The product was uniformly thinned in a 1:1 ratio in toluene.

(Z) In a similar manner, parts of solid olive oil, produced by reactingolive oil with 9% t-butyl perbenzoate in the method as described inExample 0, were liquefied by heating and compounding with the metalsoap-like reaction product obtained from heating candelilla wax withchromium carbonate (see Example 1 (f) (m) 10 parts solid cod-liver oil,produced by heating and compounding twice with 7%ditertiary-butyl-diperphthalate, were liquefied by heating andcompounding with 8 parts of the metal soap-like reaction product ofExample 1(9) (heating ouricuri wax with nickel sulfate). Theliquefaction proceeded as described above in Example :1.

(n) 3.5 parts of an insoluble substance, obtained from China-wood oil bymixing it with about 0.5% anhydrous ferric chloride and holding it ataround 50 C. for 24 hours, were reliquefied by heating and compoundingwith 8 parts of a contact substance prepared from ouricuri wax and zincbenzoate as set forth in Example 1. 3 parts of a second type ofcommercial iron napthenate (6% Fe) was added to the mixture as anadditional metal soap-like contact substance. By heating the mixtureunder stirring for 2 hours up to around 280-295 -C. a dark melt wasobtained which was dissolved in parts tetrahydronaphthalene (Tetralin)This solution was applied to a bonderized steel panel and dryed overnight in an oven at around 100 C. A coherent dry coating was obtainedwhich had a Sward hardness of around 17.

(o) 16 parts of gelled linseed oil, which was at least partiallyinsoluble in varnish solvents, like toluene, were reliquefied by heatingwith 8 parts of a greyish brown contact substance obtained from reactingup to around 270 C. 17 parts of beeswax with 3 parts of antimonytrioxide; The liquefaction of th gelled oil with this contact substancewas completed at around 265 C. and the product was thinned with toluenein the proportion of 1:1; A greenish solution was obtained which oncooling had a slightly cloudy appearance.

(p) 9 parts of at least partially insoluble and gelled solid linseed oilobtained in accordance with Example 1 were reliquefied by heating with 6parts of a Wax-type contact substance in the presence of 4 partsheat-break-stabilized linseed oil. The wax-type contact substance wasprepared by heating 12 parts carnauba wax with 2 parts magnesiumcarbonate up to about 245 C. The liquefaction was completed at around290 C. and the fused substance was thinned with 20 parts of a hydratedsolvent, tetrahydronaphthaene.

(q) 12 parts of gelled linseed oil were reliquefled by fusing together(up to around 275 C.) with 7 parts of a wax-type contact substance ataround 275 C. The liquefaction was thinned with equal parts toluene. Thewax-type substance was prepared by heating and reacting 27 parts beeswaxwith 4.5 parts bismuth benzoate heating being continued up to around 250C. A light yellowish brown substance was obtained which served as acontact substance in this example.

(1') 10 parts synthetic oil, commercial sorbitolsoybean-fatty acid-esteroil, which had been. at

least partially insolubilized by heating and com-ipounding with a freeoxygen releasing catalyst (see Example 1), and which had been freed fromits soluble oil components by heating with benzol followed by drying,were reliquefied by heating to about 280-285 C. with 5 parts of awax-type contact substance. The wax-type contact substance was producedby heating up to 270 C. and reacting 25 parts beeswax with 5 partsmanganese oxalate. As a wetting agent, 1.5 parts of a liquid syntheticwas polyethylene glycol-400-di-trie ricinoleate were added to themixture during compound heating. The resulting liquefaction was dilutedwith solvent naptha in, the proportion' of 1 part non-volatile substancewith 1.5 parts volatile matter.

(s) This example illustrates reliquefying a joint insolubilization orsolidification product obtained from reacting 26 g. linseed ,oil (typebodied oil Z-2) and 52 g. monostyrene under heating with 7 g. of a freeoxygen releasing catalyst, t-butyl perbenzoate. The reaction wasobserved at around 145 C. and 51.5 g. solids were obtained. These solidswould not dissolve in hot toluene, they would not form a coherent film,and did not melt when put on the heated surface of a conventionalcovered laboratory electric hot plate. On heating 5 parts of thesesolids with 11 parts of a contact substance prepared from 30 partspolyethylene glycol-400-di-tri-ricinoleate and 5 parts chromium oxalateby heating and compounding from 200 to around 275 C., the linseedoil-styrene solids were reliquefied. The product was soluble in equalparts toluene. In applying the solution to a steel plate and dryingiitaround 100 C. over night, a coherent film formation was obtained.Liquefaction occurred upon heating at 250 C. for about minutes andstopping the heating at 270 C.

(t) 8 parts heat-gelled long-oil alkyd gel, prepared by heating 18 partsof a commercial longoil alkyd (Glyptal 2475), in an open vessel ataround 280300 C. until a, strong gel had been formed, were liquefied byheating and reacting with 14 parts of a metal soap-like contact substance prepared by heating 42 parts polyethylene glycol 400di-tri-ricinoleate with 7 parts zinc formiate. Liquefaction of the gelwas accomplished at around 270 C. The product was readily dissolved inequal parts benzol.

(u) 11 parts of a partially solidified, partially gelled and at leastpartially insoluble long-oil alkyd product was prepared by heat reactinga long-oil plastic alkyd (Aroplaz 1085) in the presence of 540% t-butylhydroperoxide. The product was liquefied by heating with 14 parts of thecontact substance used in the previous example. The product wasliquefied around 260 C. and was readily soluble in VMP petroleumnaphtha.

(1)) 15 parts of the same at least partially insoluble long-oil alkydwere liquefied by heating and compounding with 6 parts of the contactsubstance prepared as in Example 1 by heating 25 parts of beeswax with 5parts manganese oxalate up to about 270 C. Liquefaction was accomplishedat around 250 C. and was completed around 265-275 C. The product wasdissolved in equal parts toluene.

(w) 15 parts of solidified, incoherent substance which was at leastpartially insoluble in varnish solvents like benzol, petroleum solvents,hydrated solvents, etc., was produced by heat-reacting a shortoil-modified alkyd resin (in this case com- Inercial Rezylresi 3112-5.in. the presence of 7% t-butyl-perbenzoate. The solidification wassolubilized after moistening with parts volatile toluene and heating'and compounding with 8 parts of the contact substance prepared byheatreacting parts ouricuri wax with 3 parts aluminum borate as setforth in Example 1. Liquefaction was completed around 280 C. and theproduct was dissolved in equal parts tetrahydronaphthalene (Tetralin).

(m) 16 parts of gelled and at least partially insoluble linseed oil wereresolubilized by heating and compounding with 10 parts of a contactsubstance produced from 25 parts di-ethylene glycol monolaureate, asynthetic wax type composition, and 5 parts cobalt acetate as in Example1 (12). The resolubilization occurred at around 260 C. and heating wascontinued up to about 275 C. The product was completely dissolved in-parts solvent naphtha.

Example 3 The following examples illustrate the resolubilization of atleast partially insolubilized waxes and. gelled wax derivates by meansof contact substances derived from natural and synthetic oils inaccordance with the aforementioned application S. N. 748,665.

(a) 10 parts of partially insolubilized carnauba wax, a natural plantwax were liquefied by heating and compounding with ten parts of acontact substance obtained by compounding 93 parts linseed oil with 1.5parts cobalt acetate at a temperature somewhat above 200 C. The carnaubawax and the linseed oil type contact substance were heated andcompounded, liquefaction occurring at around 240 C. Heating wascontinued up to about 280 C. and the product was thereafter dissolved intwo parts VMP petroleum naphtha, thereby resulting in a stable state ofsolution. The resulting solution was applied to a bonderized steelpanel, dried by baking at 120 C. for 45 minutes and then aged for 24hours at 50 C. A dry film coating was obtained on the steel panel.

In another application, 55 parts of the product solution were combinedwith 48 parts of a paste consisting of 20 parts lead formate, 10 partsred lead, 4 parts zinc oxide, 11 parts linseed oil (type Z-2) and 3parts VMP petroleum naphtha. The resulting paint compound was applied toa steel panel and baked and aged as in the case of the precedingexample. The resulting film had a Sward hardness of 6. V

(b) 10 parts of at least partially insoluble animal wax; namely,spermaceti wax, were liquefied by heating and compounding with 10 partsof a contact substance obtained by melting and compounding 50 parts of asorbitol-soybean fatty acid ester with 4 parts manganese carbonate atabout 200 C. The partially solidified spermaceti wax and the contactsubstance were heated and compounded to about 220 C. until the reactionsubsided and a uniform liquid was obtained. The resulting compositionwas substantially completely dissolved in equal parts benzol.

(c) 10 parts of at least partially insolubilized montan wax, a naturallignite wax, were liquefied by heating and compounding with 6 parts oflinseed oil type contact substance as used in Example 3 (a) above. Inorder to increase the wetting capacity of the contact substance on thesolidified montan wax, 10 parts toluene were added. As heating wascontinued the solvent evaporated, but was not replaced since it was onlyinitially of benefit in increasing the wetting capacity of the catalyston the solidified montan 1'4 wax. Liquefaction was obtained at around270 C. and heating was continued up to around 290 C. The resultingcomposition was diluted with 15 parts xylene.

(d) 16 parts of an at least partially insolubilized synthetic wax;namely, polyethylene glycol-di-tri-ricinoleate, was resolubilized byheating and compounding with an oil-type contact substance obtained bycompounding and heating parts of linseed oil and 2 parts of iron oxide,as set forth in the aforementioned copending application S. N. 748,665.The insoluble synthetic wax and the contact substance were heated andcompounded up to a temperature of about 240 C. at which timeliquefaction was obtained. Heating was continued to 260 C. and theresulting composition was then thinned with 2 parts toluene.

(e) 10 parts partially insoluble beeswax were liquefied by heating andcompounding with 9 parts of a contact substance obtained from reacting93 parts of soybean oil with 6 parts lead acetate at about 240 C. Thecompounds were heated under stirring to about 250 C. whereupon uniformliquid state was observed. Heating was continued to about 270 C. and theproduct uniformly thinned with a mixture of 10 parts solvent naphtha and10 parts toluene.

(f) 10 parts partially insoluble carnauba Wax were liquefied aftermoisting with 10 parts of a volatile solvent, in this case xylene, byheating and compounding with 8.5 parts of a contact substance (obtainedfrom reacting 40 parts soybean oil with 6 parts nickel sulfate graduallyup to 250 C. and above). In the liquefaction process, the liquid statewas observed at around 260 C. Heating was continued up to 290 C. and theproduct was uniformly thinned with 20 parts toluene.

(g) 10 parts of at least partially insoluble solvent purified Japan waxwere reliquefied by heating with 20 parts of a contact substanceobtained from heating 30 parts of dehydrated castor oil with 9 partszinc formiate up to around 250 to 260 C. whereby a light yellowish brownproduct was obtained. The mixture of the wax and the prepared contactsubstance was heated to around 285 C. under stirring. The liquefiedreaction product was completely dissolved in 50 parts xylene and a truesolution was obtained.

(h) 8 parts of partially insoluble carnauba wax,

which had been purified three times by boiling with toluene followed bydrying at C. for 3 days, wer reliquefied by heating and compounding themup to 310 C. with 10 parts of a greenish colored contact substanceobtained by heating 25 parts commercial lard oil (X-298) with 6 partscopper oxalate up to around 280 C. The liquefaction of the carnauba waxwas completely dissolved in 25 parts benzol.

(i) Beeswax, obtained from reacting 50 parts crude beeswax under heatingwith 9 parts t-butyl perbenzoate and purified by heating with 500 partstoluene and by filtering off the undissolved at least partiallyinsoluble solid wax from the toluene solution and dried over night at100 C., was used in this example. The treated beeswax does not melt attemperatures up to about 300 C. But it was made fusible by heating andcompounding up to 240 C., 6 parts of this wax with 10 parts of a contactsubstance derived from heating 10 parts of teaseed oil with 3.5 partslithium mono-hydroxide. Under very strong foaming, a reddish browncompound was formed which remained liquid under heating and was decantedfrom a small residue of unliquefied crystalline substance. The resultingcontact substance and the prepared beeswax were'heated under stirring upto 295 C. and formed a fused, liquid compound. 1

In a similar manner, 6-parts of the same prepared beeswax were fusedinto aliquid state by heating with 15 parts of another contact substancedrived from heating 20 parts soybean oil with 5 parts silver nitrate upto around 290 C. The contact substance was dark and cloudy inappearance.

(1') 8 parts of at least partially insoluble carnauba wax were fused andliquefied by heating and compounding with 10 parts of a contactsubstance obtained from heating 26 parts soybean oil with 5 partsantimony oxide up to 280 C. A slightly yellow liquefaction was obtained.

(is) 10 parts of at least partially insoluble beeswax were liquefied byheating with 13 parts of a contact substance obtained from heating andcompounding 23 parts cod-liver oil with 4 parts bismuth benzoate up toabout 260 C. This contact substance was a dark brown material whichshowed some sedimentation of unreacted bismuth benzoate. Liquefactionwas obtained on heating the prepared wax and the contact substance up to295 C. under stirring. The resulting solution in equal parts xyleneappeared as a greenish brown compound. I

(Z) 4 parts at least partially insoluble ouricuri wax were liquefied byheating and compounding with 6 parts of a contact substance obtainedfrom heating 20 parts menhaden fish oil with 4.5 parts chromic acetateup to around 255 C. This contact substance had a blueisli brown colorand showed that some unused surplus of metal salt remained undissolved.The wax was liquefied with this contact substance on heating andcompounding at around 275-285 C. The resulting around 265 C., a lightcolored oil was decantedv and used for the liquefaction of the wax.Liquefaction was completed at around 285 C. and 1:1 toluene solution wasmade up, which was light colored and wax-like in appearance aftercooling. (0) 9 parts of anat least partially insoluble ouricuri wax werereliquefied by heating. and compounding with 10 parts of a contactsubstance produced by reacting 12 parts of a synthetic commercial oil(Neo Fat 17) based on C22 acids, with 2 parts magnesium carbonate.reaction subsided around 260 C. after strong foaming and on cooling, thereaction product was a solid wax-like material. In the liquefyingprocess, heating and compounding was carried up to about 290 C. A darksolution was obtained which was diluted with two parts hydrated solvent(Tetralin) (p) 5 parts at least partially insoluble polyethyleneglycol-di-tri-ricinoleate were liquefied by using a metal soap-likecontact substance derived from a synthetic fatty acid-ester of aresinous polyhydroxyl alcohol (the commercial esterification ofdehydrated castor oil with Epon The uct was obtained, which was used asthe contact substance: 5 parts of the treated synthetic waxlikesubstance, 8 parts of the contact substance and 5 parts of the initialliquid synthetic wax-like substance, the latter being added as a wettingagent, were heated and compounded up to about 280 C. A liquefied,uniform product was obtained which was dissolved in equal parts xylene.The resulting solution produced a coherent film when baked onto a steelpanel.

(q) 12 parts at least partially insoluble ouricuri wax, obtained byreacting ouricuri wax with about 8-11% t-butyl perbenzoate under heatingand compounding'up to around C. and followed by solvent extraction ofthe residual soluble matter with benzol, were solubilized by heating andcompounding with 16 parts contact substance produced from beeswax andmanganese oxalat as described in Example 1. Liquefaction was obtained ataround 280 C. and the product was readily dissolved in equal partstoluene.

(1") 7 parts of the same ouricuri wax were liquefied by heating with 7parts of a contact substance produced from ouricuri wax and zincbenzoate according to Example 1. The liquefaction was performed up toaround 285 C. and the prod not was directly dissolved in one andone-half parts xylene.

(s) 8 parts of the same ouricuri wax were liquefied by heating up toabout 255 C. with 8 parts of a wax-type contact substance. tactsubstance was obtained by heating and reacting 18 parts carnauba waxwith 3 parts basic aluminum acetate as described in Example 1,

The liquefaction was thinned with equal parts xylene. After cooling, thesolution had a soft wax-like appearance.

(t) 8 parts of an at least partially solidified polyethyleneglycol-400-di-tri-ricinoleate were moistened with 4 parts toluene andthen com-' pounded and heated up to 265 C. for about 40 minutes with 9parts of a wax derived contact substance. This contact substance wasproduced from heating and reacting 18 parts carnauba wax with 3 partsaluminum acetate up to about 280 C. At room-temperature it appeared as awax-like coherent solid. The liquefaction of the solids was diluted witha' hydrated solvent (commercial Hexalin) in the proportion of 1 partnon-volatile On cooling, a slightto 1 part volatile substance. ly waxysolution was obtained.

(u) 10 parts at least partially insoluble ouricuri wax were liquefied byheating up to about 260 C. and reacting with 10 parts of a contact ducedfrom heating a mixture of candelilla wax and China-wood oil withmagnesium carbonate,- as in Example 1. The liquefaction was produced.

in the presence of 1.5 parts of soybean oil under heating up to about265 C. The compound was. readily dissolved in one and one-half parts.

xylene.

(w) 10 parts of the same ouricuri wax were llquefied by heating andcompounding with 8 The con- 17 parts of a contact substance produced byheating and reacting beeswax'with manganese oxalate. The liquefactionwas complete at around 280 C. and was readily dissolved equal part inbenzol.

(:c) 6 parts of at least partially solidified wool fat, a wax-typeanimal product, were liquefied by heating with 11 parts of a contactsubstance produced from heating and reacting 12 parts carnauba wax with2 parts magnesium carbonate. To increase the initial contact between thetwo substances, 6 parts of a volatile solvent (xylene) were added.Heating and compounding were continued up to about 270-280 C. and theprodnot was thinned with solvent naptha inthe proportion of 1 partnon-volatile matter with 2 parts solvent.

(1/) 10 parts of solidified and at least partially insolublepolyethylene glycol-400431-tri-ricinoleate were liquefied by heatingwith 9 parts of a contact substance (produced under Example 1 from thesame material in its liquid soluble state and chromium oxalate). Thewetting of the solids was facilitated by adding at the start 3 partsvolatile solvent (xylene) and the liquefaction was completed at around250 C. The prodnot was readily dissolved in equal parts toluene.

(z) The preceding example was repeated with a contact substance producedfrom the reaction product of 57 parts of the liquid synthetic wax with10 parts bismuth benzoate, and similar results were obtained.

(ca) 3.5 parts at least partially insoluble beeswax, as used in earlierexamples, were solubilized by heating and compounding in the presence of1 part liquid soybean oil with 7 parts of a contact substance. Thiscontact substance was produced by heating and reacting 20 parts of apolyhydroxyl alcohol fatty acid phthalic acid-ester compound, that is anoil-modified alkyd (commercial Rezyl 310-), with 3 parts aluminum borateuntil foaming subsided at around 255 C. A light brown reaction productwas obtained.

(bb) 3.5 parts of the same beeswax was liquefied in the presence of 1part soybean oil by heating and compounding with '7 parts of saidcontact substance until liquefaction was obtained at around 250 C. Theproduct was thinned with 1.4 parts hydrated solvent (commercialHexalin).

(cc) 10 parts of a solidified polyethyleneglycol-400-di-tri-ricinoleatewere liquefied with 10 parts of a contact substance produced from along-oil-modified alkyd (commercial Glyptal 2475), by reacting andcompounding parts thereof with 2.5 parts chromium carbonate up to270-280 C. The liquefaction of the solid synthetic w'ax was completedaround 255 C., heatme being continued up to 280 C. The product wasdissolved in equal parts benzol. A light colored solution was obtained.

(dd) 8 parts treated ouricuri wax, as used in previous examples, wereliquefied by heating and reacting with 8 parts of a contact substanceprepared from a plastic-type, long-oil modified alkyd (commercialAroplaz 1085 plastic). The contact substance was prepared by heating andcompounding 54 parts of this alkyd with 10 parts lead acetate up to 260C. and a light brownish product was obtained which was of a resin-likeappearance at room temperature. Liquefaction of the wax was completedaround 270 C. and the product was readily dissolved in equal parts VMPpetroleum solvent.

Example 4 The ronowmg exampis exempiuy the r'solu- 18 bilization of atleast partially insoluble waxes by heating and compounding therewithcontact substances of the wax-type prepared in accordance with Example 1above.

(a) 10 parts of an at least partially insolubilized spermaceti wax, anatural wax, was used in the crude form in which it contained a gelled,partially solidified portion. The contact substance used in thisinstance was of the shellac wax type prepared in accordance with Example1(b) above. To intensify the solubilizing reaction, 10 parts of awetting substance, in this instance, a synthetic oil, namely, syntheticsorbitol-linseed fatty acid esterification product, known commerciallyas Atlas oil G 875 was used. Liquefaction was obtained at around 250 C.The resulting composition was thinned with 1.5 parts toluene solvent.

(b) 50 parts of at least partially solidified insoluble natural wax,spermaceti wax in this instance, was .resolubilized with parts of acontact substance produced from a synthetic wax in accordance withExample 1, above. In this instance, the contact substance comprised ametal (soap formed from polyethylene glycol-ditri-rincinoleate andcobalt acetate. Liquefaction oi the solidified spermaceti wax with thesynthetic contact substance was obtained at about 200 C. and theresulting composition was thinned with a two-part compounded solventconsisting of half xylene and half petroleum naphtha.

(c) 20 parts of solidified and at least partially insoluble montan waxwere resolubilized by heating and compounding with 10 parts of a-contact substance produced as set forth in Example 1(0), in this instance,a montan wax type contact substance. The heating and compounding wascontinued under stirring up to about 300 C. at which time liquefactionoccurred. The reulting composition was thinned with 40 parts benzolsolvent. A clear solution was obtained which upon application to a metalsurface in the form of asteel panel gave a flat and uniform coating upondrying. In a. similar test with a cobalt meta-1 soap contact substanceof the mon tan wax type, a finished film coating on a steel panel wasexposed to mineral oil (Shell grade Diala oil #15) and heated to betweenand C. It was observed that the film was not attacked by the oil up tothis temperature.

((1) 20 parts of an at least partially insolubilized synthetic wax, inthis instance, diethylene glycol mono-laureate (known commercially asGlaurin) were liquefied by compounding and heating with 20 parts of acontact substance derived from shellac wax and red lead oxide as setforth in Example 1(1)) above. The liquefaction was carried out in thepresence of 10 parts of diethylene glycol mono-laureate utilized as awetting agent for increasing the contact between the solid and thecontact substance. Liquefaction occurred at about 250 C. The resultingcomposition was thinned by adding 2.2 parts of toluene solvent, thesolvent being added after the liquefaction had been cooled to about theboiling temperature of the solvent.

in this instance, the reaction product of a polyethyleneglycol-di-tri-ricinoleate and cobalt acetate. The solidified syntheticwax and the synthetic wax type contact substance were heated andcompounded up to about 270 C. at which point the liquefaction wasobserved. The resulting composition was thinned in an equal amount oftoluene solvent.

i (f) This example exemplifies the liquefaction of an at least partiallyinsoluble wax by utilization of mixture contact substance derived froman oil.

V 10 parts of insolubilized carnauba wax were resolubilized by heatingand compounding with a mixture of 12 parts of contact substance obtainedfrom the reaction product of 93 parts linseed oil and 2.5 parts ironoxide plus 6 parts of contact substance in the form of a reactionproduct obtained from 60 parts beeswax with parts basic bismuthacetate.'the latter having been prepared in accordance with Exampleabove. The liquefaction of the insoluble carnauba wax with the mixtureof contact substances. consisting of both an oil type and a wax type,was accomplished at around 225 C. Heating was continued to about 250 C.and the resulting composition was diluted with 40 parts xylene solvent.

(9) 21 parts partially insolubilized Japan wax were liquefied by heatingand compounding with 17 parts of a metal soap-like reaction productwhich had been produced by heating 58 parts Japan wax with 5 partslithium hydroxide (Example l(h)). Li uefaction occurred at around 250 C.and heating was continued to around 290 0. Upon cooling the product wascompletely diluted with 40 parts benzol.

(h) 10 parts partially solidified beeswax were resolubilized by heatingand compounding with a contact substance comprising 4 parts of thereaction product of the Example 1 (g) (ouricuri wax and nickelsulfateland 3'parts of the reaction product from Example 10) (candelillawax and chromium carbonate). The solubilizing reaction was completedaround 280 C. and the product was uniformly thinned with 20 parts ofxylene.

(i) In another test, 10 parts solidified, partially insoluble montan waxwere reliquefied by heating and compounding with 9 parts of a metalsoaplike reaction product obtained from heating 39 parts of Japan waxwith 6 parts silver nitrate (Example 1(i)). Liquefaction was observedaround 245 C. Heating was continued to around 280 C. and the product wasthinned in a 1:1 ratio with toluene.

(i) parts of the solidified and at least partially insoluble montan waxwere reliquefied by heating them with 12 parts of the metal soaplikereaction product of Example 1(f) (which consisted in reacting 45 partsof candililla wax with 5 parts chromium carbonate). Liquefaction wasobtainedaround and above 275 C. The produce was diluted with 30 parts ofthe hydrated solvent, namely a commercial Hexaline.

(k) 12 parts partially insolubilized synthetic wax, in this instancepolyethylene glycol di-triricinoleate,- were liquefied by heating andcompounding with 10 parts of a contact substance comprising the reactionproduct produced in Example 10') from Japan wax and aluminum sulfate.The liquefaction was obtained at around 255 C., and heating wascontinued to about 275 C. The product was uniformly thinned with Pa s.0xy e-,.,.; r. V V l (n 10 arts of an at least partially solidifieddiethylene glycol monolaureate were liquified by up to about 255 C. andthe product was com-;

pletely thinned with equal parts benzol.

Example 5 The following examples exemplify the resolubilization of atleast partially insoluble waxes by means of contact substances of thefree acid type.

(a) In exemplifyingthe use of a fatty acid, 6 parts solidified beeswaxin its crude form were resolubilized by treatment with 3 parts fattyacid contact substance; namely, a commercial copper oleate. Liquefactionof the solidified beeswax with the fatty acid contact substance occurredaround 220 C. The product was dissolved in 10 partstetrahydronaphthalene. On cooling the product to room temperature, itthickened to a wax-like form, but was readily dissolved upon slightwarming by thinning with about 10 additional part solvent.

(b) 5 parts solidified di glycol stearate, recovered after a solventpurification, were resolubilized with 10 parts commercial leadnaphthenate containing about 24% lead. 4 parts of a volatile VMP naphthawhich evaporated during the liquefaction heating were used as a wettingsubstance. The liquefaction was obtained at about 240 C. The product wasdissolved in 15 parts of toluene and remained liquid at roomtemperature.

(0) In this example, a naphthenate type substance, commercial cobaltnaphthenate containing about 6% cobalt was used as a contact substance.15 parts solidified, at least partially insoluble American montan waxwas obtained by heating 54 parts thereof with a free-oxygen releasingcatalyst comprising 7 parts tertiary butyl Derbenzoate untilsolidification occurred at about 260 C. The 15 grams solid montan waxwas heated and compounded with 13 parts of the cobalt naphthenatesubstance in addition to '7 grams mineral spirits being added as avolatile solvent wettingagent. The mineral spirits evaporated duringheating and reaction was observed at about 130 0. Heating was continuedand at around 230 C. all the solid montan wax appeared to have beensolidified. Heating under stirring was continued to about 250 C. Theresulting composition was dissolved in 60 parts benzol and the solutionthereof was applied on a steel panel in the form of a film which wasbaked at about 0., whereby a permanent film of considerable gloss wasobtained.

In a similar example, solidified montan wax was liquefied with a montanwax type contact substance and a film was prepared on a steel panel asin the preceding example. The film was tested for its resistance tomineral oil (Shell grade Diala oil 15 being used). It was noted that thefilm was not attacked by the oil until thetemperatur-e exceeded 0., thusillustrating the film-forming characteristics of the resolubilized Waxformed in accordance with the present process from initially solid andinsoluble wax.

(d) In this instance a rosin acid type contact substance was utilized,the contact substance benr par dirom rosin acid and; ma ganes at leastpartially insolubilized-shellac was were reliquefied by heating withparts manganese resinate in the presence of 2.5 parts linseed "oil usedas a wetting substance. Liquefaction was obtained at about 230 C. andthe product was dissolved in 20 parts xylene solvent.

(e) In this instance, a nickel resinate contact substance was utilized.5 parts of at leastpar tially insolubilized solid carnauba'w'a'xin itscrud'e form were resolubilized by heating with-a mixture of 3.5 partsnickel resinate contact substance plus 1.5 parts of a shellac wax-redlead contact substance as obtained in Example 1(b) above. The solidcarnauba wax and the mixture of the nickel resinate and shellac waxcontact substances were heated and compounded in the presence of 2 partscorn oil used as -a wetting substance. Liquefaction occurred around245C. and the product was dissolved in parts toluene solvent.

(f) 2.8 parts solidified carn'auba wax were'resolubilized by heatingwith parts of a solution consisting of 10 parts of calcium naphth'enate(4% calcium) contact substance in 10 parts of VMP naphtha. The solventused as a wetting substance evaporated during the heatingand at about225 C. liquefaction was obtained. The reaction product was dissolved in10 parts toluene.

(g) In another test, the liquefactionproduc't of a solidified montanwax, obtained by treatment with cobalt naphthenate, was thinned withtoluene in a 1:1 ratio and this solution was further diluted with 3times the amount of a ketone solvent, in this casemethyl-iso-buty-l-ketone, which is a preferred solvent for variousgroups of coating materials. A clear solution was obtained whichremainedstabledurin'g 2 weeks storage at room temperature. a. In another test, 5parts "solidified montan wax was mixed with 20 parts solid linseed oilas described in Example 2(0), and this mixture was liquefied by heatingand compounding with 30 parts of .a commercial naphthenate, in this caselead naphthenate (24% lead). Again the reaction product was thinned withparts toluene. Afterwards the resulting solution was "further dilutedwith 40 parts methyl-iso-butyl ketoneand a-stable, clear solution wasobtained.

(h) :5 parts of solidified and 'at least partially insoluble beeswaxwere moistened with 2 parts toluene. As a contact substance, a mixture"of 5 parts commercial calcium naphthenate solution (5% Ca) and 7 partscommercial zinc naphthanate solution (8% Zn) were added. The com poundwas heated up toabout 275 C. for about 45 minutes and a fused mass wasobtained. This mass was dissolved in 20 parts tricresylph'o'sphater Oncooling, a soft, waxy soluble substance was obtained.

(i) 18 parts of at least partially solidified and insolubilized andnon-fusible beeswax were liquefied by heating and compounding with 7parts non-volatile cobalt octoic metal soapcontact substance and 13parts volatile matter. To facilitate the wetting '7 parts of toluenewere added. In this instance, commercial cobalt octoid drier (6% Co) andobtained in a solution with 35% nonvolatile matter was used.Liquefaction of the solids was observed at around 275 C. and heating wasdiscontinued at around 295 C. The product was dissolved in 25 partstoluene and a clear blue solution was obtained. This solution wasclearly miscible in equal parts methyl-ism butyl ketone. It was alsoclearly miscible with equal parts monostyrene.

"(ii :16 parts gelled linseed :oiiwere heated with 5.5 partsnen-volatile cobalt=octoic acid product in the presence of10partsvolatilemaitter. The melting product "was held between 275 and290 C. 'for about 30 minutes until complete liquefaction had beenobtained. The resulting product was readily diluted with equal partstoluene. The liquefied wax from the preceding example was mixedin equalparts with this solution of the liquefied oil gel and clear solutionswereob'tained.

- Example'o The following examples exemplify the resolubilization of amixture of at least partially insolubl waxes and at least partiallyinsoluble oils.

25 parts of a-solidified wax substance, namely. polyethyleneglycol-di-tri-r-icinoleate were added to 3.5 parts of a solidified oilproduct, namely,- solidified.sorbitol-linseed fatty acid ester (knowninthe commercial form as Atlas Oil G 875). The mixtureof the oil and waxinsoluble substances were solubilized by heating and compounding with6.9 .parts of a contact substance consisting of a mixture of 5.5 partslithium naphthenate and 1.4 parts manganese naphthenate (6% Mn) Theliquefaction was accomplished in the presence of 1.5 parts soluble oil;in this instance, the soluble sorbitol-linseed fatty acid ester wasused. The liquefaction was obtained at about 260 C. The product wasdissolved in a mixture of 6 parts coal tar solvent, namely, toluene, and10 parts hydrated solvent, namely, deka-hydro-naphthalene.

Example 7 In order to exemplify the addition of pigments, colors, etc.,inorder to modify the process and products of the present invention,forus-e in the coating and impregnating arts, the solubilized productobtained in Example 3(a), namely, soluble carnauba wax, was pigmentedwith 'a piga merit compound consisting of a mixture of 35 parts leadchromate, 17 parts red leadan'dB parts zinc oxide. This pigment wasground into the soluble carnauba wax until a normal paint consistencywas obtained and additional amounts of naphtha were added to enable theapplication of auniform coating. The resulting paint composi-'- tion wasapplied to panels which were dried for '45 minutes at C. and "a dryuniform coating was obtained.

In accordance with the present invention it has been found that thesolubilization of at least partially soluble gelatini'zed natural orsynthetic waxes or natural or synthetic oils, or combina= tio'nsthereof, may be accomplished with waxty e or oil-type contactsubstances, or both, in the presence of other materials such asasphalt's, noh-gelatiziized o'ils, none1aunized waxes, resins, sums,synthetic resinous materials; such as phenolic resins, alkyd resins andthe like. It will also be understood that the final products of thepresent invention may besuppleme'nted or modified by the addition ofothei' -oleo or resinous compounds, pigments, etc., for improving theirapplication and use in the coating and impreg hating arts. Thus, thephysical propertiespsuch as hardness, elasticity, color affinity, acidresistance, drying conditions and the like may be improved by theaforementioned additions. In addition, the resulting compositions of thepresentinvention may be hardened or solidified by-the addition ofvulcanizing or accelerating .agents. Additionally, theeompositions ofthe present in vention may also be u'sedlas plasticizers fcrresma 23 buscompounds;-lacquers such as cellulose lacquers, plastic compoundsand thelike.

It will be understood that the melting temperatures utilized to compoundand solubilize the insoluble wax-type compounds or the insolubleoil-type compounds, or both, with either the oiltype or the wax-typecontact substance, or both,

decomposition. Thus by virtue of the present invention, it is possibleto form a soluble resulting composition which is capable of forming astable solution, and one which is capable of being further diluted withthe usual coal tar and petroleum solvents. Moreover, the solubilizedfinal product is capable of being heated without gelatin'ization and isfurther capable of being regelatinized into a gel or other solid formsby utilization of a freeoxygen releasing catalyst in the mannerdescribed in my pending application Ser. No. 33,676. Additionally,itshould be pointed out that the resulting regelatinized andresolidified product resulting from reaction with a free-oxygen yieldingcatalyst may again be solubilized by means of the process of the presentinvention.

The present process'has the further advantage that natural and syntheticwax compositions and natural and synthetic oil compositions may bedecolorized and purified; that is, they may be freed of undesirablecomponents in the solid state and in an at least partially solid stateand can thereafter be resolubilized in accordance withthe presentinvention for use in the coating and impregnating arts.

A further advantage resulting from the present invention is thatliquefactions of the insoluble wax or oil compounds can be producedwhich are in the form of soluble solids at room temperatures prior todilution or thinning with the usual solvents. Thus, these soluble solidscan be kept easily; stored and shipped in a soluble solid form and canthereafter readily be dissolved in sole vents and diluted for use in thearts.

Still another advantage of the present inven tion is that since thesolubilized wax type or oil type products can be liquified in suchmanner that their melting point is considerably higher than that of theoriginal soluble waxes and oils as commercially obtained in the naturalsynthetic state, and since such melting'point can be modified byaltering the ratio of the insoluble oil. or wax to the contactsubstance, and further by adding varying amounts of preferred componentsas heretofore mentioned, it is thereby possible to produce impregnatingand insulating compounds,

24 produce solubilized and liquefied products which are practically freefrom such additional compounds which make them incompatible with otherwaxes, oil or resins. In this manner it is possible to produce clear andsoluble solutions.

which are free from undesired materials.

The wax or oil base compositions of the presentinvention may be used forthe preparation of varnishes, lacquers, coatings. extrusions, coverings,modifiers for resinous materials, impregnations for cloth and the like.They may also be used for producing electrical insulating mate-.

rials, such as'binding materials for fiber bindings, in addition tobeing used for heat and moisture insulating materials and as laminatingcom alcohol having more than two hydroxy groups which comprises meltingand compounding with said ester a compound comprising a metal'soap of ahigher fatty acid ester of an alcohol having from one to two hydroxygroups at a melting temperature below the decomposition temperature ofthe resulting composition and at such melting temperature thatsubstantiallythe entire mass of, the resulting composition is meltedinto the liquid stage, whereby to form a soluble ester reaction productcapable of forming a stable solution.

2. The method set forth in claim 1 wherein the at least partiallyinsoluble higher fatty acid ester of a polyhydric alcohol comprises suchan ester of a trihydric alcohol.

3. The method set forth in claim 1 wherein the at least partiallyinsoluble higher fatty acid ester of a polyhydric alcohol comprises asynthetically produced oil-like ester of a higher fatty acid.

4. A method of solubilizing an at least partially insoluble oil selectedfrom the group consisting of fixed oils and synthetically produced oilscontaininga higher fatty acid ester of a polyhydric melting temperaturethat substantially the entire mass of the resulting composition ismelted into e l q d wh reby to form a soluble oil reaction productcapable of forming a stablesolu ion.

5. The method set forthin claim 4 wherein the metal soap compoundcomprises a metal soap of a higher fatty acid ester of a dihydricalcohol.

6. The method set forth in claim 4 wherein the metal soap compoundcomprises a metal soap of a higher. fatty acid ester of a mono-hydricalcohol.

'7. The method set forth in claim 4 wherein the metal soap compoundcomprises a metal soap of a synthetically produced wax-like ester of ahigher fatty acid.

8. A method of solubilizing an at least partially insoluble higher fattyacid ester of a polyhydric alcohol having more than two hydroxy groupswhich comprises melting and compounding with said ester a compoundcomprising a metal soap of a wax at a melting temperature below thedecomposition temperature of the resulting compo-f sition and at suchmelting temperature that sub-.- stantially the entire mass of theresulting composition is melted into the liquid stage, whereby to form asoluble ester reaction product capable of forming a stable solution.

9. The method set forth in claim 8 wherein the metal soap compoundcomprises a metal soap of an animal wax.

10. The method set forth in claim 8 wherein the metal soap compoundcomprises a metal soap of a vegetable wax.

11. The method set forth in claim 8 wherein the metal soap compoundcomprises a metal soap of an insect Wax.

12. A method of solubilizing an at least partially insoluble oilselected from the group consisting of fixed oils and syntheticallyproduced oils containing a higher fatty acid ester which comprisesmelting and compounding with said oil a compound comprising a metal soapof a wax at a melting temperature below the decomposition temperature ofthe resulting composition and at such melting temperature thatsubstantially the entire mass of the resulting composition is meltedinto the liquid stage, whereby to form a soluble ester reaction productcapable of forming in a stable solution.

MAX KRON STEIN.

No references cited.

4. A METHOD OF SOLUBILIZING AN AT LEAST PARTIALLY INSOLUBLE OIL SELECTEDFROM THE GROUP CONSISTING OF FIXED OILS AND SYNTHETICALLY PRODUCED OILSCONTAINING A HIGHER FATTY ACID ESTER OF A POLYHYDRIC ALCOHOL HAVING MORETHAN TWO HYDROXY GROUPS WHICH COMPRISES MELTING AND COMPOUNDING WITHSAID OIL A COMPOUND COMPRISING A METAL SOAP OF A HIGHER FATTY ACID ESTEROF AN ALCOHOL HAVING FROM ONE TO TWO HYDROXY GROUPS AT A MELTINGTEMPERATURE BELOW THE DECOMPOSITION TEMPERATURE OF THE RESULTINGCOMPOSITION AND AT SUCH MELTING TEMPERATURE THAT SUBSTANTIALLYI THEENTIRE MASS OF THE RESULTING CVOMPOSITION IS MELTED INTO THE LIQUIDSTAGE, WHEREBY TO FORM A SOLUBLE OIL REACTION PRODUCT CAPABLE OF FORMINGA STABLE SOLUTION.